Shallow groundwater of the huge deltaic systems of Asia like the Red River Delta in Vietnam is often enriched in inorganic arsenic (As), threatening the health of millions of residents. The massive abstraction of groundwater in these areas locally causes an irreversible mixing of arsenic-free groundwater resources with arsenic-rich groundwater. Increased concentrations of competitive anions, especially phosphate (PO43-), decrease the immobilization capacity of the sediments. During transport, the mobility of dissolved As in local aquifers is strongly influenced by adsorption to sedimentary and ubiquitously occurring iron(oxyhydr)oxides. Additionally, arsenic-rich groundwater is often enriched in reduced iron (Fe2+) as well, which is capable to react with iron(oxyhydr)oxides, thereby inducing mineral transformations. Such transformations permanently affect the arsenic adsorption and immobilization capacity of the sediments.Within the scope of this research project, the underlying mechanisms related to As transport and the resulting threat to arsenic-free groundwater resources will be characterized in cooperation with the Swiss Federal Institute of Aquatic Science and Technology (Eawag). The research concept aims at assessing the complex interactions within the arsenic-iron-phosphate-system under field conditions at a study site next to the Red River. First, filtration experiments using local groundwater enriched in As and PO43- will be used to determine the As adsorption capacity of different and previously geochemically characterized iron(oxyhydr)oxides. In a second step, sample carrier containing As loaded iron(oxyhydr)oxides will be introduced into surface near aquifer parts of the study site (via existing groundwater monitoring wells). These samples will be exposed to local groundwater characterized by increased As, Fe2+ and PO43- concentrations for the following nine months. Using the in situ exposition of predefined iron(oxyhydr)oxides, it will be possible to distinguish potential mineral transformations and their influences on the As immobilization capacity of the respective iron(oxyhydr)oxides. By combining the results and outcomes of the field experiments, new and important conclusions regarding the mobility of As can be drawn. The data can be used to create a hydrochemical transport model describing reactive As transport within the investigation area. In addition, the results of the in situ exposition experiments will allow to draw conclusions in respective to the long term As immobilization capacity of different iron(oxyhydr)oxides, which is an essential information regarding in situ decontamination techniques.
During microbial turnover of organic chemicals in soil, non-extractable residues (NER) are formed frequently. Studies on NER formation usually performed with radioisotope labelled tracer compounds are limited to localisation and quantitative analyses but their chemical composition is left unknown. Recently, we could show for 2,4-dichlorophenoxyacetic acid and ibuprofen that during microbial turnover in soil nearly all NER were derived from microbial biomass, since degrading bacteria use the pollutant carbon for their biomass synthesis. Their cell debris is subsequently stabilised within soil organic matter (SOM) forming biogenic NER (bioNER). It is still unknown whether bioNER are also formed during biodegradation of other, structurally different compound classes of organic contaminants. Therefore, agricultural soil will be incubated with labelled compounds of five classes of commonly used and emerging pesticides: organophosphate, phenylurea, triazinone, benzothiadiazine and aryloxyphenoxypropionic acid. The fate of the label will be monitored in both living and non-living SOM pools and the formation of bioNER will be quantified for each compound over extended periods of time. In addition, soil samples from long-term lysimeter studies with 14C-labelled pesticide residues (e.g. triazine, benzothiazole and phenoxypropionic acid group) will be also analysed for bioNER formation. The results will be summarised to identify the metabolic conditions of microorganisms needed for bioNER formation and to develop an extended concept of risk assessment including bioNER formation in soils.
When released into surface waters, engineered inorganic nanoparticles (EINP) can be subject to multiple transformations. The objectives of MASK are to understand under which conditions EINP in aquatic systems will attach to suspended matter, under which conditions and in which time scale EINP are coated by NOM present in freshwater systems, how these coated colloidal particles are stabilized in the aquatic system and to which extent the aquatic aging processes are reversible. Homo-aggregation, coating changes, biological interactions and hetero-aggregation are hypothesized as key processes governing EINP aging in water bodies. In process orientated laboratory incubation experiments (50 ml to 6 l) with increasing complexity, MASK unravels the relevance and the interplay of inorganic colloids, aquagenic and pedogenic organic matter and solution physicochemistry for stability of EINP. These systems will successively approach situations in real waters. MASK thus provides information on EINP fluxes in the aquatic compartment, their time scales, reversibility and relative relevance. EINP will be analysed by standard light scattering techniques, ICP-MS, ESEM/EDX, WetSTEM and AFM. A method coupling hydrodynamic radius chromatography (HDC) with ICPMS recently developed by K. Tiede for nAg0 will be optimized and developed for further EINP analysis, MASK is further responsible for the virtual subproject ANALYSIS, the development and optimization of joint research unit methods of EINP analysis, sample preparation and sample storage, the exchange of methods and coordinates the joint analyses and the central EINP database.
In this project we experimentally explore the transport of engineered inorganic nanoparticles (EINP) through soils. This is done for original EINPs and some pre-aged form. Transport of NPs in soil is expected to be different from that of reactive solutes, in that hydrodynamic drag, inertial and shear forces as well as the affinity to water-gas interfaces are expected to be more relevant. Hence, the mobility of EINPs in soil is highly sensitive to the morphology of the porous structure and the dynamics of water saturation.This project provides the pore network structure for natural soils using X-ray micro-tomography to allow for an up-scaling of pore-scale interactions explored by project partners to the scale of soil horizons. The pore structure is represented by a network model suitable for pore scale simulations including the dynamics of water-gas interfaces.Pore network simulations will be compared to column experiments for conservative tracers as well as for unaltered and pre-aged EINPs (obtained from INTERFACE). This includes steady state flow scenarios for saturated (ponding) and unsaturated conditions as well as for transient flow to explore the impact of moving water-gas interfaces. The final goal is to arrive at a consistent interpretation of experimental findings and numerical simulations to develop a module for modelling EINP transfer through soil as a function of particle properties, soil structural characteristics and external forcing in terms of flux boundary conditions.
Zielsetzung und Anlass des Vorhabens: Ziel der letzten Projektphase war es, mit einer Langzeit-Praxiserprobung das zweistufige biologische Verfahren zur Deponiesickerwasserreinigung als Stand der Technik zu etablieren und zu bilanzieren. Nach der Inbetriebnahme des Technikums am Deponiestandort Schöneiche ging es in der zwölfmonatigen Laufzeit des Projektes AZ 14996/04 in den Langzeitversuchen um die Validierung der Laborergebnisse im technischen Maßstab, die verfahrenstechnische Optimierung der Anlage und um eine damit verbundene mögliche Kostenreduzierung des Systems. Darstellung der Arbeitsschritte und der angewandten Methoden: Nach dem ersten Technikums-Probebetrieb wurde eine Reihe von Optimierungsmaßnahmen durchgeführt: - der Umbau des Rohsickerwasserzulaufs, - die Verwendung von Soda statt Bicarbonat für die Ammoniumoxidation in Reaktor 2, - der Einsatz von Membrandosierpumpen mit integrierten Rückschlagventilen für die Zugabe von Soda und Essigsäure, - der Einbau von zusätzlichen Polyurethan-Festbetten zur Vergrößerung der Oberfläche für die Besiedlung mit Mikroorganismen, - die Einstellung des Sollwerts für Reaktor 4 auf einen pH-Wert von 6,5, - ein Update der SPS-Steuerung der Nanofiltration zur freien Programmierung der Spülzyklen, - der Einbau eines Absperrhahns vor den Nanofiltrations-Vorfilter - und die Trennung des Nanofiltrationsablaufs vom Reaktoren-Sammelablauf zur Behälterleerung. Es wurde sowohl Rohsickerwasser der MEAB-Deponie Schöneiche als auch Sickerwasserkonzentrat der Deponie Vorketzin behandelt. Fazit: Wegen der durchgeführten Optimierungsmaßnahmen ist es prinzipiell gelungen, das Schöneicher Rohsickerwasser gemäß Anhang 51 der Abwasserverordnung aufzureinigen. In Vorketzin wurde die organische Belastung über 70% und Stickstoff über 80% reduziert. Nach Rückgang der Calciumfracht sollte es zukünftig möglich sein, mit der Zweistufen-Biologie das Sickerwasserkonzentrat ausreichend zu reinigen, da organische Belastung und Stickstoffgehalt geringer als im Schöneicher Rohsickerwasser sind. Um das Verfahren als Stand der Technik, vor allem für die Behandlung von Sickerwasserkonzentraten, zu etablieren, müssten die Laborvorgaben mit den Erfahrungen des Technikumsbetriebs kombiniert und in einer weiteren Versuchsreihe unter optimierten Bedingungen verifiziert werden.
Chromium (Cr) is introduced into the environment by several anthropogenic activities. A striking ex-ample is the area around Kanpur in the Indian state of Uttar Pradesh, where large amounts of Cr-containing wastes have been recently illegally deposited. Hexavalent Cr, a highly toxic and mobile contaminant, is present in significant amounts in these wastes, severely affecting the quality of sur-roundings soils, sediments, and ground waters. The first major goal of this study is to clarify the solid phase speciation of Cr in these wastes and to examine its leaching behavior. X-ray diffraction and synchrotron-based X-ray absorption spectroscopy techniques will be employed for quantitative solid phase speciation of Cr. Its leaching behavior will be studied in column experiments performed at un-saturated moisture conditions with flow interruptions simulating monsoon rain events. Combined with geochemical modeling, the results will allow the evaluation of the leaching potential and release kinetics of Cr from the waste materials. The second major goal is to investigate the spatial distribution, speciation, and solubility of Cr in the rooting zone of chromate-contaminated soils surrounding the landfills, and to study the suitability of biochar as novel soil amendment for mitigating the deleterious effects of chromate pollution. Detailed field samplings and laboratory soil incubation studies will be carried out with two agricultural soils and biochar from the Kanpur region.
Organotin and especially butyltin compounds are used for a variety of applications, e.g. as biocides, stabilizers, catalysts and intermediates in chemical syntheses. Tributyltin (TBT) compounds exhibit the greatest toxicity of all organotins and have even been characterized as one of the most toxic groups of xenobiotics ever produced and deliberately introduced into the environment. TBT is not only used as an active biocidal compound in antifouling paints, which are designed to prevent marine and freshwater biota from settlement on ship hulls, harbour and offshore installations, but also as a biocide in wood preservatives, textiles, dispersion paints and agricultural pesticides. Additionally, it occurs as a by-product of mono- (MBT) and dibutyltin (DBT) compounds, which are used as UV stabilizer in many plastics and for other applications. Triphenyltin (TPT) compounds are also used as the active biocide in antifouling paints outside Europe and furthermore as an agricultural fungicide since the early 1960s to combat a range of fungal diseases in various crops, particularly potato blight, leaf spot and powdery mildew on sugar beet, peanuts and celery, other fungi on hop, brown rust on beans, grey moulds on onions, rice blast and coffee leaf rust. Although the use of TBT and TPT was regulated in many countries world-wide from restrictions for certain applications to a total ban, these compounds are still present in the environment. In the early 1970s the impact of TBT on nontarget organisms became apparent. Among the broad variety of malformations caused by TBT in aquatic animals, molluscs have been found to be an extremely sensitive group of invertebrates and no other pathological condition produced by TBT at relative low concentrations rivals that of the imposex phenomenon in prosobranch gastropods speaking in terms of sensitivity. TBT induces imposex in marine prosobranchs at concentrations as low as 0,5 ng TBT-Sn/L. Since 1993, for the littorinid snail Littorina littorea a second virilisation phenomenon, termed intersex, is known. In female specimens affected by intersex the pallial oviduct is transformed of towards a male morphology with a final supplanting of female organs by the corresponding male formations. Imposex and intersex are morphological alterations caused by a chronic exposure to ultra-trace concentrations of TBT. A biological effect monitoring offers the possibility to determine the degree of contamination with organotin compounds in the aquatic environment and especially in coastal waters without using any expensive analytical methods. Furthermore, the biological effect monitoring allows an assessment of the existing TBT pollution on the basis of biological effects. Such results are normally more relevant for the ecosystem than pure analytical data. usw.
The nature of the microbial communities inhabiting the deeper soil horizons is largely unknown. It is also not clear why subsurface microorganisms do not make faster use of organic compounds under field conditions. The answer could be provided by a reciprocal soil transfer experiment studying the response of transferred soils to fluctuations in microclimate, organic inputs, and soil biota. The subproject P9 will be responsible for the establishment of reciprocal transfer experiments offering a strong link between subgroups interested in organic matter quality, transport of organic substances, as well as functions of the soil microbial community. A single, high molecular weight substrate (13C labelled cellulose) will be applied at two different levels in the pre-experiment to understand the dose-dependent reaction of soil microorganisms in transferred surface and sub-soils. Uniformly 13C labelled beech roots - representing complex substrates - will be used for the main reciprocal soil transfer experiment. We hypothesize that transferring soil cores between subsoil and surface soil as well as addition of labelled cellulose or roots will allow us to evaluate the relative impact of surface/subsurface habitat conditions and resource availability on abundance, function, and diversity of the soil microbial community. The second objective of the subproject is to understand whether minerals buried within different soil compartments (topsoil vs. subsoil) in the field contribute to creation of hot spots of microbial abundance and activity within a period of two to five years. We hypothesize that soil microorganisms colonize organo-mineral complexes depending on their nutritional composition and substrate availability. The existence of micro-habitat specific microbial communities could be important for short term carbon storage (1 to 6 years). The third objective is to understand the biogeography and function of soil microorganisms in different subsoils. Parent material as well as mineral composition might control niche differentiation during soil development. Depending on size and interconnectedness of niches, colonization and survival of soil microbial communities might be different in soils derived from loess, sand, terra fusca, or sandstone. From the methodological point of view, our specific interest is to place community composition into context with soil microbial functions in subsoils. Our subgroup will be responsible for determining the abundance, diversity, und function of soil microorganisms (13C microbial biomass, 13C PLFA, enzyme activities, DNA extraction followed by quantitative PCR). Quantitative PCR will be used to estimate total abundances of bacteria, archaea and fungi as well as abundances of specific groups of bacteria at high taxonomic levels. We will apply taxa specific bacterial primers because classes or phyla might be differentiated into ecological categories on the basis of their life strategies.
Soil structure determines a large part of the spatial heterogeneity in water storage and fluxes from the plot to the hillslope scale. In recent decades important progress in hydrological research has been achieved by including soil structure in hydrological models. One of the main problems herein remains the difficulty of measuring soil structure and quantifying its influence on hydrological processes. As soil structure is very often of biogenic origin (macropores), the main objective of this project is to use the influence of bioactivity and resulting soil structures to describe and support modelling of hydrological processes at different scales. Therefore, local scale bioactivity will be linked to local infiltration patterns under varying catchment conditions. At hillslope scale, the spatial distribution of bioactivity patterns will be linked to connectivity of subsurface structures to explain subsurface stormflow generation. Then we will apply species distribution modelling of key organisms in order to extrapolate the gained knowledge to the catchment scale. As on one hand, bioactivity influences the hydrological processes, but on the other hand the species distribution also depends on soil moisture contents, including the feedbacks between bioactivity and soil hydrology is pivotal for getting reliable predictions of catchment scale hydrological behavior under land use change and climate change.
Dairy farming across Germany displays diverse production systems. Factor endowment, management, technology adoption as well as competitive dynamics in the local or regional land, agribusiness and dairy processing sectors contribute to this differentiation on farm level. These differences impact on the ability of dairy farms and regional dairy production systems to successfully respond to pressures arising from future market and policy changes. The overall objective of the research activities of which this project is a part of, is to develop a thorough understanding of the processes that govern the spatial dynamics of dairy farm development in different regions in Germany. The central hypothesis of this research project is that management system and technological choices differ systematically across local production and market conditions. The empirical approach will focus on the estimation of farm specific nonparametric cost functions for dairy farms located in across Germany differentiated by time and location. A spatially differentiated data base with information on input use, resource availability, as well as local market conditions for land and output markets will be compiled. The nonparametric approach is specifically suited to disclose a more accurate representation of dairy production system heterogeneity across locations and time compared to parametric concepts as it provides the necessary flexibility to accommodate non-linearities relevant for a wide domain of explanatory variables. The methodology employed goes beyond the state of the art of the literature as it combines kernel density estimation with a Bayesian sampling approach to provide theory consistent parameters for each farm in the data sample.The specific methodological hypothesis is that the nonparametric approach is superior to current parametric techniques and this hypothesis is tested using statistical model evaluation. Regarding the farm management and technological choices, we hypothesize that land suitability for feed production determines the farm intensity of dairy production and thus management and technological choices. With respect to the ability of farms to successfully respond to market pressures we hypothesize that farms at the upper and lower tail of the intensity distribution both can generate positive returns from dairy production. These last two hypotheses will be tested using the estimated spatially differentiated farm specific costs and marginal costs.The expected outcomes are of relevance for the agricultural sector and the food supply chain economy as a whole as fundamental market structure changes in the dairy sector are ongoing due to the abolition of the quota regulation in the years 2014/2015. Thus, exact knowledge about differences and development of dairy cost heterogeneity of farms within and between regions are an important factor for the actors involved in the market as well as the political support of this process.
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